Process for the preparation of cement, mortars, concrete compositions containing a calcium carbonate—based filler (pre)—treated with a superplasticizer, compositions and cement products obtained and their applications

ABSTRACT

The invention concerns a PROCESS for the preparation of cement/mortar/concrete (for simplicity: “cement”) compositions or systems, (hereafter “cement” compositions or systems for simplicity), of a general known type, in which the filler(s) is/are comprising or consist of “calcium carbonate-based filler(s)”, comprising at least one step where the said filler(s) is/are treated with an efficient treating amount of at least one treating agent consisting of or comprising superplastifier(s). The main purpose of this invention is to build a process aimed at providing improved, “High performance”, FLUID, cement or mortars or concrete systems or compositions having an improved compacity, an improved flowability, and globally speaking a definitely improved “workability”, and “regularity” of the properties of the final systems. The present invention also concerns a filler for “cement” compositions, characterized in that if consists of, or comprises, a calcium-carbonate-based filler or blends of same, pre-treated with an “efficient amount” of at least one superplastifier.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation of U.S. application Ser. No. 13/813,977, filedMar. 18, 2013, which is a U.S. National phase of PCT Application No.PCT/IB2011/001927, filed Aug. 23, 2011, which claims priority toEuropean Application No. 10008803.8, filed Aug. 24, 2010, and U.S.Provisional Application No. 61/414,508, filed Nov. 17, 2010, thecontents of which are hereby incorporated by reference.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to the field of cement compositions,cementitious compositions, hydraulic binders compositions, mortarcompositions, concrete “compositions” (or hereafter equivalently“systems”), namely of the type compositions (or “systems”) ofcement/hydraulic binders, mortars, concrete, containing at least oneparticulate mineral of the calcium carbonate(s) type as a filler, andtheir applications, as well as the corresponding cement, mortar,concrete products or elements, the said filler being “upgraded”according to the invention to a “technical” or “high performance” (“HP”)level of performance due to a process which is the essential part of theinvention.

The invention relates to a specific process for producing the saidcompositions or “systems” (those terms are going to be used asequivalents in this application and claims) for cement, hydraulicbinder, mortar, concrete, the obtained compositions, the cement, mortarsand concrete products obtained therefrom, and their applications.

PRIOR ART

It is reminded that a cement system (or equivalently “composition”) is asystem comprising cement particles, mixing water (or equivalently amixing aqueous composition not interfering with the said system, asknown to the skilled man), filler(s), various optional and usualadditives such as air entrainment agents, setting retarders, settingaccelerators and the like, and any such routine additives as well knownto the skilled man.

A mortar system additionally contains an inert aggregate material,usually a sand.

A concrete system still additionally contains gravel.

The above is abundantly known and common knowledge.

As a matter of simplicity, and also because the invention relates to theuse of additives adapted to improve or “upgrade” the properties of anyof those three systems, the terms “cement systems” (or “compositions”)will be used in the following to encompass ANY of the above three mainkinds of compositions or “systems”, that is a cement, cementitious,hydraulic binder, mortar or concrete composition or system. The skilledman will be able to appreciate if the system is a cement, a mortar or aconcrete composition in view of the presence, or the absence, of sandand/or gravel. This simplification is made possible since sand andgravel are inert materials, and therefore do not noticeably interferewith the invention.

It is also pointed out that, even if, in the following, an informationis provided regarding “cement systems” for example, it ALSO appliesmutatis mutandis to any of the four other kinds of systems. The onlydifference between the systems being the presence, or not, of sandand/or gravel.

In such compositions, fluidifier(s) is/are often used.

In that domain, the EP 0 663 892 to CHRYSO is certainly the mostrelevant document, which discloses fluidifier polymers for mineralsuspensions with no hydraulic setting, or hydraulic binders slurries.

Cited applications are paper coating, paints, and synthetic resins orrubber compositions.

According to the said prior art, it was known to add fluidifiers inmineral, particular suspensions to lower their viscosity, and,especially for paper applications, this leads to high mineralconcentrations, a better workability, and this reduces the dryingenergy. For example, this is used in connection with suspensions ofcalcium carbonate.

It is also known to add such fluidifiers to “cement” (in the wide senseexplained hereabove) slurries, with the purpose this time of reducingtheir water content and to obtain a “cement” composition with a “moredense structure” after setting.

Encountered problems are: the influence of electrolytes, which reducesthe fluidifying effect and forces to increase the amount of fluidifier(with an increase in cost), as well as, for “cement”, the need not tonegatively alter the setting characteristics of the cement compositionnot its final properties.

Some well-known fluidifiers are superplastifiers or plastifiers.

In that domain, the EP 0 663 892 to CHRYSO is relevant, as well as FR 2815 627, FR 2 815 629 and WO2008/107790 which also disclose interestingsuperplastifiers.

Some known fluidifiers affect less the setting time, but are stillunsatisfactory, such as condensation products of sulfonated naphtaleneand formaldehyde or melamine-formaldehyde with a sulfonated compound.Some of those products are also superplastifiers, but much lesspreferred.

Also, EP 0 099 954 relates to fluidifiers made by condensation ofamino-sulfonic acid comprising at least an aromatic ring withnitrogenated compounds bearing several amine functions and formaldehyde.

Such are said not to delay too much the setting of cement compositions,but they are highly sensitive to electrolytes when it comes to their“activity”. They also can be obtained with low concentrations, usuallyno more than about 40% by dry weight, since any concentration increasein turn increases their viscosity to inadmissible levels.

The summary of the desired properties is listed page 3 lines 15 ff ofthe above-mentioned EP.

It is also known to add filler(s) in cement, hydraulic binders,cementitious or concrete or mortars compositions or “systems”.

The purpose of adding such filler(s) is to fill the voids betweenparticles, to reduce the overall costs, and to greatly improve aproperty called “consistency” (consistency being the capacity or abilityfor the considered systems to easily flow or “self-level”, or not) and aproperty called “compacity” (that is the percentage of dry material inthe final composition (the higher the percentage, the better thecompacity)).

In the present invention, the said usable filler(s) is/are defined as“calcium carbonate-based filler(s)” that is, in this application andclaims, contain(s) only calcium carbonate(s) (possibly of variousorigins, such as various natural rocks or various PCCs) which means withno other filler of a different type, such as kaolin, bentonite, etc.known to the skilled man, and is/are preferably provided (when thefiller(s) is/are or contain(s) GCC(s)) by a carbonated rock or moregenerally mineral material(s) comprising at least 50-65% by weight (dry)of CaCO₃, preferably more than 80%, still more preferably more than 90%;those filler(s)s are selected among:

-   -   natural calcium carbonate(s) or ground calcium carbonate(s)        (GCC(s)) such as, non limitatively, GCC from marble, chalk,        calcite, or from other natural and well-known forms of natural        calcium carbonates which preferably meet the above % criteria;        -   PCC(s) which is a precipitated calcium carbonate, and exists            under various well-known forms, depending on the well-known            precipitation/preparation process.        -   or a mixture of said CaCO₃-containing rocks or mineral            materials with each other as well as blends or mixtures of            GCC(s) and PCC(s).

The GCC/PCC ratio can be chosen from 0-100 to 100-0% by dry weight,preferably from 30-70 to 70/30% by dry weight.

Usually a “filler” has the following properties:

-   -   Purity (methylene blue test) is lower than 10 g/kg, preferably        below 3-5 g/kg, preferably below 1-1.5 g, with a most        interesting value at 1.2 g/kg.    -   Mean diameter or d₅₀ is about in the range of 1-3 to 30-50        micrometers measured by using the Malvern 2000 PSD        equipment/methodology.    -   Blaine surface, which is a characteristic feature of FILLERS, as        is well-known, is in the domain of 180-2000 m²/kg, preferably of        300 to 800 m²/kg, as measured under an EU Standard (European        standard EN 196-6).

As is known, a “cement” (in the above mentioned wide sense) compositionor “system” is mainly made of:

Cement (or cementitious composition or hydraulic binder)+mixing water(or mixing aqueous composition allowing setting but not interfering withthe system)+optionally (usually inert) particulate and/or fibrousfiller(s)+inert agglomerate(s) such as optionally sand+optionally inertgravel (plus optionally well known additives not to be mentioned indetail nor in full in the present application, such as settingaccelerators, setting retarders, air entrainment agents, etc. . . .)+miscellaneous “routine” additives aimed at matching the precise needof the end-user.

Aggregates such as sand, inert gravel or “all-in” aggregates are knownmaterials so commonly used that no description is needed here.

As discussed above, the invention relates also equivalently (under thegeneric term “cement” for simplicity) to mortars compositions or“systems” (like above including an aggregate like sand but no gravel)and cement compositions (same as above but no gravel and no sand).

“Mainly” means here that the system may contain some impurities ortraces of additives or adjuvants, not to be mentioned in the presentapplication, such as air entrainment agents, accelerators, retarders,etc.

“Mixing water” will mean in this patent application plain mix water oraqueous mixing compositions, that is mainly water plus usual additives,allowing the normal setting of the “cement” compositions, withoutinterfering with the other properties of the overall composition, oronly, via the additives, to improve some usual properties.

“Fillers” in this invention have been precisely defined hereabove, thatis fillers containing under any known form (namely GCCs and/or PCCs),only CaCO₃ particulate material, plus optionally some other inert fillerparticles or fibrous material such as hemp etc., BUT no other type offiller such as kaolin, bentonite etc., and their various blends.

In this whole application and claims, “inert” shall mean a materialwhich has no noticeable (or negligible) impact or interference with theprocess of the invention and the obtained compositions, products andapplications. Given the involved ingredients, this will be easilyappreciated by any skilled man.

The prior art “cement” (in the wide sense as defined above) systems todate are therefore mainly made of:

Cement (or hydraulic binders or cementitious compositions)+mixing water(or mixing aqueous compositions not interfering with thesystem)+optionally aggregate(s) such as sand+optionallygravel+FILLER(s)+“routine” additives.

It is also known that cement/hydraulic binders/cementitiouscompositions, cements, mortars and concrete compositions can bebasically sorted out into:

DRY systems (poor quality or “low”) (casting is performed with highvibration and energy).

PLASTIC systems (medium quality) (medium vibration and energy).

FLUID systems (High performance or “HP”) (low vibration and low energy).

A very simple test is used to classify the systems, using a “mini cône àchape” known as “self-levelling test” or “screed flow cone test”.

The test is well known and is conducted as follows, according to therecognized Standard EN 196-1; the said standard defines accurately themixer or kneading (also malaxing) device to be used, the speed ofrotation, and each and every such data useful for reproducing the test.Therefore, no more explanations or definitions are needed here for thesake of clarity or reproducibility.

For simplification, “cement” will encompass in this whole applicationnot only cement material, but also cementitious compositions andhydraulic binders (other than cement) compositions, and their blends. Asindicated above, it also encompasses corresponding mortars andconcretes.

Self Levelling Test:

Basically, a cement or mortar or concrete “system” is prepared by mixingthe above ingredients according to usual practice, recalled here-belowin more detail though the process conditions are well known, then ispoured in accordance with the above Standard conditions, into aninverted cone which is perforated at its bottom (dimensions are alsogiven by the said Standard as well as each and every useful data of thetest). The cement or mortar or concrete system therefore flows into andout of the said cone, namely through its bottom aperture, and falls ontoan horizontal plate to form a “chape” (“screed”).

It there forms a “galette” or “cone” also known as “dry to plastic form”whose diameter is measured, and aspect visually inspected for examplefor stickiness and “thickness”, the latter property reflecting a “slow”or “viscous” mix, that is, if “thick”, hard to handle.

The larger the diameter, the more flowable the system. For a given highconsistency, as targeted by the invention, this is the major test.

Given the quality of the initial filler to be used in the concretesystem, namely its place of production, morphology etc. the resultingcone will vary in diameter, this indicating a variation in flowability.

As an example, a GCC which is known to use no or almost no mixing water,and shows such valuable properties, will lead to a very fluid,non-sticky cement or concrete composition. Such a composition will befully usable for “technical” (that is, “high performance” or “HP”)concrete compositions, called “FLUID” above.

If to the contrary, the filler namely GCC filler absorbs or uses anoticeable amount of water, or contains some impurities, etc. theresulting composition will be less fluid and become to be somewhatsticky. The end user will be forced inter alia to either add acorrective adjuvant (with an associated extra cost and an associatedrisk of secondary effect of the composition as a whole) and/or add extrawater (thus being detrimental to consistency and inducing associatedrisks). Those compositions will be used for medium quality compositions,called “PLASTIC” hereabove.

At the other end of the ladder, using a filler namely a GCC of poorquality will lead to a composition which will exit the mixer under theform of sticky granulates. Those will be used only for DRY concretecompositions, NOT part of the invention.

The test will be sufficient for a skilled man to rate the starting GCCand/or PCC (s). The same is valid mutatis mutandis when using a PCC or aGCC/PCC blend.

In order to provide the skilled man with useful guidelines andinformation about the meaning of “low”, “medium” or “HP” filler, weattach the TABLE A where ten fillers A to K of various origin andmorphology (as indicated for characterization by the skilled man) havebeen tested for various properties and qualities, or drawbacks, with theclassification “low” “medium” or “HP” being added on each line.

TABLE A Characterization of “low”, “medium”, “HP” fillers and theiraspect Blue (Methylene Treatment geological Blue visual Agent Codedesignation (age) Type d50 Blaine Test) (3 g) (4 g) Evaluationevaluation A white chalk facies chalk 1.0 >1400 2.0 plastic 220 lowslow, very (90 Mi) aspect thick B white chalk facies chalk 2.2 1120 2.7280 340 medium thick (90 Mi) C urgonian facies calcite 3.1 1171 0.3 200290 low slow, thick (115 Mi) D bioclastic facies calcite 6.0 720 1.0plastic 338 medium plastic (160Mi) aspect E urgonian facies calcite 6.5395 0.3 460 475 HP fluid (115 Mi) G upper jurassic marble 17.0 363 0.3dry 365 medium slow, heavy (130 Mi) aspect H upper jurassic marble 13.4385 0.3 337 413 low slow, viscous (120 Mi) I H + 5% B X X X X 190 390medium slow, viscous J H + 15% B X X X X 427 436 HP fluid K H + 20% B XX X X 340 410 medium fluid, thick

One uses 3 g or respectfully 4 g of superplastifier Premia 196commercialised by the Firm CHRYSO, and which is a commercial product ata concentration of 25.3% by weight (dry extract measured along theStandard EN 480-8), by DRY weight of cement.

In the said Table A, “+15% B” evidently means an addition of 15% of theproduct B, to form a blend or mix, the % being in DRY WEIGHT/DRY MIXWEIGHT.

Equally, columns “3g” and “4g” means that 3 or respectfully 4 g of thesaid superplastifer have been added by DRY weight of the cementcomponent alone.

“Mi” means “million years” (dating of the rock)

“Blue” means “methylene blue test” (purity test)

This introduction of this application clearly points out to the need forimproved cement or mortar or concrete systems or compositions having aimproved compacity (% of dry material, the highest possible), animproved flowability (that is forming a non sticky “galette” or “cone”of large diameter in the above described test, the larger the diameter,the better flowability), and globally speaking a definitely improved“workability” (workability being the ability of the cement or concretecomposition to be prepared, processed, handled, and used to form a highperformance or “technical” concrete) and a far better “regularity” inthe final product properties especially at the end user level. Clearly,some of those desired properties are antagonistic, and for example oneshould expect a high % dry material to perform poorly in a flowabilitytest.

Technical Problem(s) to be Solved

The main purpose of this invention is to build a process aimed atproviding improved, “High performance”, FLUID, cement or mortars orconcrete systems or compositions having an improved compacity(percentage of dry material, the highest possible), an improvedflowability (that is forming a non-sticky “galette” or “cone” of largediameter in the above described test, the larger the diameter, thebetter flowability), and globally speaking a definitely improved“workability” (workability being the ability of the cement or concretecomposition to be prepared, processed, handled, and used to form a highperformance or “technical” cements, mortars or concrete compositions orsystems).

Another property, which does not exists in the prior art, while theindustry is strongly demanding it, is “regularity” of the properties ofthe final systems.

It has been surprisingly found according to this invention, that thatset of objectives can be reached by treating the filler(s) in thespecific manner as disclosed below, with only minute amounts of treatingagents, and with a very impressive technical effect.

BRIEF SUMMARY OF THE INVENTION

The invention resides first in a PROCESS for the preparation of theabove defined cement/mortar/concrete compositions or systems, (forsimplicity hereafter “cement” compositions or systems), of a generalknown type as defined hereabove containing filler(s), in which thefiller(s) is/are comprising or consist of “calcium carbonate-basedfiller(s)” as defined hereabove, characterized in that it comprises atleast one step where the said calcium-carbonate-based filler(s) is/aretreated with an efficient treating amount of at least one treating agentconsisting of or comprising superplastifier(s).

The treatment is believed to treat only the calcium carbonate(s) part ofthe filler(s), and for example not the other particulate or fibrousfillers, IF ANY, believed to be inert in this process.

This preferred option or best mode will be named “pre-treatment” orequivalently (in the Tables 1-6 which correspond to LABORATORYexperiments where the fillers are pre-treated in a small laboratorymixer) “initial” mode.

To be noted that the “Lödige” tests mentioned in the same Tables arealso pre-treatment tests according to the invention, but performed in anINDUSTRIAL and well-known kneading or mixing device, called Lödigeequipment.

By “comprising or consisting of” we mean that the fillers may consist ofcalcium carbonate(s), optionally mixed with non interferring fillers,and that the treating agent(s) can be: only superplastifier(s) or blendsof superplastifier(s) with non-interfering plasticizer(s) (as definedherebelow) and/or routine, inert, additives.

By “efficient treating (or “treatment”) amount” or “efficient surfacecoverage of the fillers particles or grains” or “efficiently treated”,we mean in this application that at least 50%, preferably at least 60,or better at least 80 or 90% or still better closer to 100% of thesurface of the particles of the filler(s) have been subjected to aphysico-chemical interaction with the superplastifier(s). Thisphysico-chemical interaction is not entirely understood as of the filingdate, only the EFFECTS and RESULTS are duly identified and correlated tothe treating superplastifier(s), but, without being tied by any theory,the applicant considers that the said interaction or “treatment” is asurface treatment or “surface-covering” treatment involving ionic,physical, mechanical and/or chemical, treatment(s) and via saidinteraction(s). This efficient treating or treatment amount musttherefore be important enough to treat the said % of particle surfaces,as will be explained and disclosed in more detail below.

By “surface-covering” we mean that the superplasticizers are supposed bythe applicant, without being tied by a theory, to engage in electricalcharge potential interactions with the ionic charges of the surface ofthe filler, which promotes the fixation of the superplastifier ontoand/or closely around the surface and so reduces the “accessible”surface of the particle having no surface saturation of the grain bysaid treatment.

This corresponds to an “UNblocking” of the particles or grains, whatfirst “triggers” then promotes the mobility freedom of the particleswith respect to each other.

This is NOT a fluidification process: this is a “trigger action” leadingto an UNblocking process or sudden removal of interparticleinterference/friction without which the rest of the properties cannot bereached and especially not the required fluidity.

It is believed that this so “triggered” “Unblocking” function is one ofthe very key parameters allowing to appreciate the appropriate“treatment” or “surface coverage”. By “comprising” we mean in thisapplication that the treating agent can be made only ofsuperplastifier(s) (one or more mixed together, preferably one) or ofblends of superplastifier(s) displaying mutual non-interference (thatis, unable to noticeably degrade the above “treatment”) amount orproportion of known plasticizer(s) for the purpose of cost-saving, asexplained in greater detail here-below.

1. According to the best mode of the invention, as defined to date, thesaid filler(s) is/are efficiently treated before being introduced in thekneading or mixing device (“pre-treatment” also named “initial” in theTables 1-6), such as in an outside mixing Laboratory equipment; in theindustrial scale, such a pre-treatment can be performed in an industrialdevice such as the Lödige mixer or any other industrial kneading ormixing equipment known to the art.

2. According to a less preferred embodiment, the said filler(s) is/aretreated after having being introduced in the kneading or mixing device(“inside treatment”). In such a case, the said filler(s) is/areefficiently treated after having being introduced in the kneading ormixing device (“inside treatment”) with the filler(s) and the efficienttreating amount of the treating agent(s) being introduced in thekneading or mixing device either simultaneously or in a manner such thatthe filler(s) and the efficient amount of the treating agent(s) areintroduced separately BUT at a very close location and time.

3. According to another embodiment, the said filler(s) is/areefficiently treated partially before being introduced in the kneading ormixing device (“partial pre-treatment”) (such as in a well-known Lödigeequipment) and partially after having been introduced in the pre-treatedstate in the said mixing or kneading device, the total of the twopartial treatments being “efficient” in terms of treatment, surfacecoverage etc. as defined above. (“mixed treatment”), with the secondpart or amount of the treating agent(s) being introduced in the kneadingor mixing device either simultaneously with the pre-treated fillers orin a manner such that the pretreated filler(s) and the second part ofthe treating agent(s) are introduced separately BUT at a very closelocation and time.

When the filler(s) is/are to be treated at least partially inside thekneading or mixing device, (“mixed treatment”), the skilled man willunderstand that a corresponding amount or proportion of treatingsuperplastifier(s) has to be added directly into the said kneading ormixing device or in admixture with the considered filler just before theintroduction in the kneading or mixing device, in the latter case, forexample, on the weighting device (“balance”) which is provided justbefore the powdered products are introduced into the kneading or mixingdevice. “Just before” will be easily understood as a place and timewhere the filler(s) and treating agents cannot or have no time to bemixed together, what would induce the beginning of the treatment. A goodexample is the balance where the two powders are placed together thenalmost immediately introduced, with no previous kneading or mixing, intothe kneading or mixing device. It is much preferred that the point andtime of introduction of the said proportion of treating agent be asclose as possible to the point and time of introduction of the partiallytreated filler(s), so as not to be diluted in the pre-existing productsalready present in the mixing or kneading device (such as sand, gravel,mix water, optionally routine additives, so that the treating agent befully available for the filler(s).

This is also true in relation with the option “inside treatment”.

In both options, actually, if the filler is added at a location and at atime too far form the location and time of the treating agent, whateverthe order of introduction, one could shift to a treatment which would betoo late: this would actually make possible for the treating agent to be“consumed” by other ingredients before the filler is introduced, or, inthe case of a filler introduced first, lead to a late treatment that isthe “post-ajout” mode in Tables 1-6 (“post-addition” of the treatingagent(s) a certain time after the filler has been introduced; as will besee from the Tables 1-6 and FIGS. 1-6, the results are far lower thanwith a pre-treatment, a mixed treatment or an inside treatment accordingto the invention).

Any post ajout has to be avoided.

The invention also covers an industrial option characterized in that atleast a portion of the efficient amount of treating superplastifier(s),or the totality of the said efficient amount, is mixed with thefiller(s) on the weighting device (“balance”) leading to the kneading ormixing device. This can be regarded either as a simultaneous addition,or a “near-simultaneous” addition.

It is also possible to envision a process of the invention in which aportion of the filler(s) is efficiently “pretreated” and a secondportion of the fillers is efficiently treated “inside” the kneading ormixing.

Some of the above options are evidently complicated and/or requireadditional equipments or modifications of the existing equipment. Theyare therefore far less preferred, the “pretreatment or initial modebeing the most preferred.

The “best mode” to date to avoid those drawbacks is clearly to prepare apre-treated filler then to deliver it to the end user and to introduceit as such into the kneading or mixing device, most preferably after themix water and sand and gravel, if any, have been introduced and allowedto be successively malaxed as is usual in this industry (the differencebeing that, in the present invention, the filler is TREATED, while it isNOT in the prior art).

The invention also covers such a

-   -   pre-treated “calcium carbonate-based filler(s)” as a novel        industrial product,    -   to be delivered to the end user that way, optionally after any        treatment allowing to ease the transportation.

It is known, in Laboratory trials, and due to the small volumes or loadsinvolved, to sometimes first place some small amount of “fluidifiers” inthe bottom of the laboratory mixing device: some of those fluidifiersmay be superplastifiers, many are not.

However, even when some small amounts of superplastifiers-“fluidifiers”are present, they cannot “treat” the fillers “efficiently” as in theinvention, that is according to the definition given hereabove. Theymerely act as fluidifiers, so that they interact mainly with the otherfirst constituents of the load, such as sand, gravel, mix water etc.,which are malaxed together, alone, for a given period of time, so as toconveniently fluidize the particles or aggregates in the suspension; inthis operation, they are “fixed” or “consumed” by the said aggregatesparticles that precisely need to be fluidized. If they were not, therewould be no fluidification. Therefore, they are then no longer availablefor the fillers; even if, to be absolutely complete, we assume for asecond that some (mandatorily very small amount) such fluidifier werequite partially and quite marginally available, it could only quitemarginally interfere with the filler, that is in any case absolutely notwith the “efficient” treatment effect or “surface coverage” effect or“unblocking” effect generated by the superplastifiers deliberately addedin the present invention at a moment and at a time such as to reach thepoint of “efficient treatment”. Simply, the necessary “threshold” or“TRIGGER” for Unblocking could not be reached by far, and, with no“trigger”, there could be no “Unblocking” at all. No prior art everreported any improvement or upgrading which might have a relation withthe fluidizers (many of fluidizers being additionally just plastifiers,not superplastifiers); no doubt that, especially in an R&D Laboratory,if such an upgrading had been noticed, it would have been reported. Thisis simply because the “trigger” effect for “unblocking” never occurred.

In the industrial scale, one most generally uses NO fluidifiers, or insome exceptional cases in minute amounts, and in order to “fluidize” themix: there again, the fluidifiers are “used” to fluidify sand, gravel,etc. and are not available for the fillers, and therefore can in no way“trigger” the “unblocking” of the system, the essential part of theinvention.

As indicated hereabove, the said filler(s) are made of calciumcarbonate(s) or blends thereof, that is mainly GCCs or PCCs or blends ofGCCs or blends of PCCs or blends of GCCs and PCCs.

The invention also resides in the said “CEMENT COMPOSITIONS” (in thewide sense defined above) and their USE, and in the “CEMENT ELEMENTS orPRODUCTS” so obtained from the said compositions, and their USE in the“cement” industries.

By “CEMENT ELEMENTS or PRODUCTS” it is meant in this whole applicationeach and any piece of building or construction (or any piece or productfor any other industrial purpose known to the skilled man, includingoff-shore cementing, or oil wells cementing, using “cement”compositions) prepared from the said compositions.

This will be detailed herebelow.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: correspond to a surface treatment with the superplastifier Adescribed above at a dosage of such as expressed in the correspondingTable 1.

FIG. 2: correspond to a surface treatment with the superplastifier Bdescribed above at a dosage of such as expressed in the correspondingTable 2.

FIG. 3: correspond to a surface treatment by the product NRG 100 at adosage such as expressed in the corresponding Table 3.

FIG. 4: correspond to a surface treatment with the superplastifier Adescribed above at a dosage of such as expressed in the correspondingTable 4.

FIG. 5: correspond to a surface treatment with the superplastifier Bdescribed above at a dosage of such as expressed in the correspondingTable 5.

FIG. 6: correspond to a surface treatment by the product NRG 100 at adosage such as expressed in the corresponding Table 6.

DETAILED DESCRIPTION OF THE INVENTION

In a detailed and most preferred (“best mode” as of today) embodiment,the said PROCESS for preparing the said “cement” compositions or systemsis characterized (in the so-called “pre-treatment” or (in the Tables 1-6namely) equivalently “initial” mode) by

-   -   a) providing a powder of dry calcium carbonate(s) filler as        defined above as “calcium carbonate(s)-based filler”, hereafter        “filler or filler(s);    -   b) mixing the said filler(s) with an efficient treating amount        of at least one superplastifier, thus producing “pre-treated        filler(s)”,    -   c) introducing the said pre-treated filler(s) into a kneading or        mixing device already containing mix water or a composition of        mix water possibly containing routine or “non-interfering”        additives (“mix water composition”) (hereafter for simplicity        “mixing water”)    -   d) optionally adding before or after the step c), preferably        before, aggregates such as sand and/or gravel, and possibly        other “non interfering” routine additives or adjuvants,    -   e) kneading or mixing the said load during an efficient period        of time,    -   f) recovering the said “cement” composition.

By “not interfering”, it is meant not interfering or not noticeably withthe said considered treatment or inventive process.

By “efficient period of time”, it is meant a total period of timeleading to an homogeneous mixture or blend, in the order of 2-15 min,preferably, for the “standard” mixtures or blends, 30-60 s. This will bedetailed hereafter.

An example of end-user application is as follows: if the end usertargets medium or “standard” properties for its final cementcomposition, for example with a final mixing within his facilities in afixed installation etc., he will use compositions which arecorrespondingly simple that is not specifically complex or sensitive interms of routine additives, superplastifier, filler etc; therefore, theend user will have to mix for a relatively short time such as the above35-65 s.

If to the contrary the end user targets high-level or very HPproperties, he will use correspondingly more complex compositions andmore sensitive components, for example a more sensitive filler orsuperplastifier, or sensitive routine additives aimed at reaching aspecific property, etc. . . . and usually he will use less or far lessmixing water: therefore he will need to mix for a much longer time suchas the above 1-3 to 10-15 min.

Evidently, “technical” composition or system means a “HP” quality (seethe “Self levelling test” section above) or “FLUID” see above too, andby contrast a “standard” final composition means a “non-HP” quality,that is, see above, “dry” or more likely “plastic”.

In both cases, that is “technical” or “standard” compositions, and asexplained in the present application, the common objective is to reach ahomogeneous composition, also as explained specifically in the presentapplication, see below “The main essential crieteria . . . final productmust be homogeneous”.

The above working principals are well known to the skilled man and arefor completeness only. The above values and examples are to provideguidelines only, which the skilled man will be able to easily use inorder to meet the essential “main criteria”.

One will understand that it is impossible to provide examples or datafor any type of ultimate composition or ingredient, since theinteractions are complex, so are the kinetics etc. . . . but the skilledman knows about those parameters.

According to a less preferred mode, the said PROCESS for preparing thesaid “cement” compositions or systems is characterized in the“mixed-treatment” mode by

-   -   a) providing a powder of dry calcium carbonate (s) filler as        defined above    -   b) mixing the said filler(s) with a portion or part of an        efficient treating amount of at least one superplastifier, thus        producing the partially pre-treated filler (s),    -   c) introducing the said partially pre-treated filler(s) into a        kneading or mixing device already containing mix water or a        composition of mix water possibly containing routine additives        (“mix water composition”) (hereafter for simplicity “mixing        water”)    -   d) introducing before or during step c), preferably during, into        the said kneading or mixing device, the rest of the said        efficient treating amount or proportion of the        superplastifier(s)    -   e) optionally adding before or after the steps c) and d),        preferably before, aggregates such as sand and/or gravel, and        possibly other routine additives not interfering with the said        treatment,    -   f) kneading or mixing the said load during an efficient period        of time    -   g) recovering the said “cement” composition.

According to still another embodiment, the said PROCESS for preparingthe said “cement” compositions or systems is characterized in the“inside-treatment” mode by

-   -   a) providing a powder of dry calcium carbonate (s) based        filler(s) as defined above    -   b) introducing the said un-treated filler(s) into a kneading or        mixing device already containing an efficient treating amount of        at least one superplastifier, (or receiving it just after the        introducing of the said un-treated filler(s)) mix water or a        composition of mix water possibly containing routine additives        (“mix water composition”) (hereafter for simplicity “mixing        water”)    -   c) kneading or mixing the said load during an efficient period        of time    -   d) optionally adding before or after the step c), preferably        before, aggregates such as sand and/or gravel, and possibly        other routine additives or adjuvants, not interfering with the        said treatment,    -   e) recovering the said “cement” composition.

By “just after” it is meant that the treating agent can be introducedbefore of after the un-treated filler(s), bur in the second case it mustbe introduced rapidly after the filler(s), say, in a matter of someseconds to 10 s or so, in order for the filler to remain fully availablefor the treating agents without any disturbance due to the kneading ormixing with sand, gravel etc.

It is usually most preferred to first introduce the aggregates such assand and gravel into the kneading or mixing device, and mix themoptionally with a small amount of water and/or of fluidifier (seeabove), before performing the other steps.

As treatment agent, is used at least one superplastifier (and possiblyat least one superplasticizer with possibly some inert amount ofplasticizer).

According to the above definition of the treating agent, the so calledtreating agents for the fillers consist of/or comprisesuperplastifier(s), or comprise at least one superplastifier (andoptionally at least one plastifier in order to reduce the overallcosts), and preferably consist of at least one superplastifier andoptionally at least one efficiently cost-reducing amount of plastifier,and most preferably one superplastifier and optionally one efficientlycost-reducing amount of a plasticizer.

Superplastifiers are well-known agents and are to the best selectedamong the following products or families and their blends:

Polycarboxylates, polycarboxylate ethers, or much less preferredproducts manufactured from sulfonated naphthalene condensate orsulfonated melamine formaldehyde. The skilled man knows these products,which are additionally disclosed in the prior art as cited above.

In this invention, the best mode treating agents (product A and productB) appear to be, in the superplastifiers families, of thepolycarboxylate ether formulae.

To be noted, the products codes A to K in Table A are FILLERS to becharacterized, NOT to create a confusion with the preferred treatingagent(s) A and B above which are (superplastifiers(s)).

By “efficient period of time” it is meant here a period of time of about35-65 s for the standard compositions, and from 1-3 to 10-15 min. forthe more “technical” that is more complex and/or more sensitivecompositions, as is known from the skilled man. For a “standard”composition, an example can be a kneading time of 10-15-20 s for thegravel and sand (dry kneading or mixing is preferred), then of 10 s forthe kneading or mixing of the hydraulic binder and untreated filler,then 10-15 s for the kneading or mixing with the treatment agent(s) andmix water (this in the so-called “inside treatment mode”), then 5-15 sfor the final kneading or mixing with the final “routine additives”.

The main and essential criteria for the said “period of mixing” is thatthe final product must be homogeneous and the treating agent(s) be notabsorbed or adsorbed onto the sand or gravel, or the less possibleextent.

By “efficient amount” of plasticizer (when present with thesuperplastifier) it is meant in this application an amount or proportionof plastifier which is able to reduce the cost of the treatment withoutinterfering negatively with the system and namely the filler(s)behaviour, namely in terms of surface activity and reactivity); the samecriteria applies to the “inert additives”.

By “comprising” we mean here that the said treatment agents consistessentially or entirely of superplastifier(s) as defined, and maycontain as explained a cost-reducing efficient amount of at least oneplastifier, and may also contain inert additives useful for the intendedfinal application, such as anti foam agents, retarders, acceleratorsetc. absolutely known to the skilled man.

Usual additives of inert nature can be added at injection points knownto the skilled man, as said earlier.

The mixing or kneading device can be operated in a batch mode, asemi-continuous mode, or a continuous mode, the adaptations being withinthe easy reach of an average skilled man.

Actually, it has been surprisingly discovered that suchsuperplastifier(s) previously used as mere “fluidifiers” are able toUPGRADE FILLERS from medium, and sometimes from low, to HP grade.

Dosage of Superplastifier(s) Used for the Pre-Treatment and Treatment ofthe Filler(s)

At the end-user location, the dosage in superplastifier(s) is rangingfrom 0.3 to 3 kg for 100 kg of cement, preferably 0.8 to 1.2 kg/100 kgof cement, on a DRY/DRY basis.

In laboratory conditions, the same proportion ranges from 0.05 to 0.1%by weight of the carbonate (DRY) that is 0.1 to 0.3 kg/100 kg of cement,on a DRY/DRY basis.

In laboratory conditions, for establishing the Table A, one used from0.8 to 1.1 kg/100 kg cement, on a DRY/DRY basis.

At the end user location, the ratio superplastifier(s)/plasticizer(s)can be from 100/0 to 95/5-90/10, preferably no less than 85/15 on aweight dry basis.

The invention also resides in the said CEMENT (in the broad sense givenabove that is cement, cementitious compositions, mortars, concretes)COMPOSITIONS (OR SYSTEMS):

-   -   per se, since they are distinguishable from the prior art        similar compositions by their physical structure and their        properties,    -   or as prepared by the above process of the invention,        and in the USE of those cement systems or compositions for        making concrete elements,        and ultimately in the CEMENT ELEMENTS    -   per se, since they are distinguishable for the same reasons as        the compositions,    -   and as prepared by using the said compositions.    -   as well as in the        -   calcium carbonate-based filler(s) as pre-treated by the            pretreatment process of the invention.

Another objective is evidently to meet Client's requirements which arethat the “galette” or “cone” be above 250 mm in diameter, mostpreferably 300 mm, or still better, above 300 mm, at a cost-effectivedosage.

Some filler-containing compositions meet that requirement, depending onthe origin of the filler. This can be easily and quickly appreciated bya skilled man by performing the cone and plate test.

This test allows therefore to discriminate the fillers and select thebest-performing filler and even the best performing superplastifier(s),in view of the final properties required by the end user.

Many do not meet that requirement, certain by far.

Usually (PRIOR ART PROCESS) the test is conducted on an UNtreated filler

In the present application the superplastifiers are used as treatmentagents for the filler in a specific and inventive process.

Another objective of the invention is therefore to upgrade medium or lowquality, filler-containing, cement/mortar/concrete (for simplicity,“cement”) compositions or systems to HP (or high performance)compositions, by introduction in the mixing/kneading device of the saidsuperplastifier(s) and optionally (see above) at least one cost-reducingefficient amount of plastifier(s) in order to improve the behaviour ofthe filler(s) and therefore of the overall composition.

Plastifiers(s) are selected preferably among those cited above.

Those families are very well known to the skilled man. The merit of theinventors was not to discover those families, nor their use assuperplastifiers in the common sense of the prior art, but to discoverthat one can WIDELY UPGRADE A CEMENT FILLER (and hence the cementcompositions) BY TREATING the Calcium Carbonate-based fillers with suchspecies.

It has been noted that certain compositions are so low in cone diameter(“self levelling test”), stickiness, etc. that there is no way toupgrade them; this demonstrates the difficulty of the invention's task.

Some can be upgraded but only by adding large proportions of thesuperplastifers used according to the invention and even in such cases,the diameter requirement can be matched, BUT the “galette” or “cone”remains sticky and thick in consistency, what means that the result,despite the fact that the diameter of the “galette” is correct, thecomposition cannot be regarded as upgraded to HP concrete composition.

It is necessary to keep in mind that, for a concrete composition orsystem to be acceptable as HP composition, or upgraded from low ormedium quality to HP quality, TWO features MUST be met simultaneously:

-   -   the diameter of the “galette” or cone must be above about 250,        or better above 300, or still better above 350 mm, AND    -   the “galette” or cone must NOT be sticky or thick in        consistency.

This is another measurement of the very tough challenge which thisinvention wishes to overcome, and of the very high technical andscientific input brought by the invention to the current state of theart.

As can be seen from the attached Table A, the “poor” fillers can NOT beupgraded since they never meet BOTH features.

This is also true for some “medium” fillers such as product D, B, G, Iand K which may show a good fluidity for example at a dosage of 4 g BUThave a bad aspect or handling behaviour.

With the help of the Table A and of the above and below comments, theskilled man will be able to discriminate the fillers which CAN beupgraded by the invention, and those (regarded as “low” as per the testof the Table A) which can NOT.

To achieve these objectives, the skilled man bears in mind first that acertain water/cement ratio is directly linked to the workability of thecomposition and that it is also imperative to develop high performancequalities in the end product, such as high performance or “technical”level of setting properties, drying properties, mechanical strength,namely compressive strength etc.

As specified above, the invention relies first on the surface treatmentof the CaCO₃-based FILLER(s) by one or more superplasticizer(s)(optionally in admixture with one or more plastifier). The amount ofplastifier will be calculated easily by the skilled man as being theefficient cost effective amount, not interfering with the overalltreatment, see above.

Two superplastifiers products are providing the best results. They arethe “best mode” as of the filing date (products A and B of thepolycarboxylate ether family) as mentioned above.

It is very surprising to notice that when using the invention,proportions of superplastifier(s) treating agent(s) for the CaCO₃filler(s) as low as 0.03 or 0.05 to 0.1% are sufficient. It is entirelysurprising to notice that such minuscule amounts of treating agents arecapable of upgrading to HP quality even medium to poor fillers.

Many such plasticizers, superplasticizers or fluidifiers, are known,such as described for example in the CHRYSO patent EP 0 663 892

Other products have been successfully tested as superplastifiers) usablein the process of the invention to perform a surface treatment of thecarbonate filler, such as the CHRYSO™ products described in the abovecited EP patent, such as PREMIA 196™, or NRG 100 from Mappei™.

Some usual additives may be routinely added such as air entrainmentagents, setting retarders or accelerators etc. at a place which is knownfrom the skilled man, for example with the water or after thesuperplastifiers are added.

As to the “powders” that is the cement and the filler, the cement can beadded first, then the filler, or the reverse, or they can be introducedtogether as a premix.

It is however preferred to introduce the cement and the filler togetheras a premix, so as to better ensure that both powders will behomogeneously mixed with and wet with the water.

The above are batch modes.

One can also think of continuous modes such as performing the additionin one of the above orders, for example in a kneading or mixing deviceequipped with an endless screw (with additions at various points alongthe length of the equipment), possibly with pre-mixes being added atsome point(s), or as another example in a series of successive kneadingor mixing devices, also with the possibility of adding premix(es) in oneof the devices. It will be obvious to the skilled man that especiallythe latter option (several kneading or mixing devices) has numerousdrawbacks, if only the necessary space and investment.

Batch modes are preferred and will be referred to here-below.

Routine tests can help the skilled man to select the most appropriate,in view of the available equipment, of the end user practice, and withthe help of the following Tables and Figures which are attached to thisapplication.

Tables 1, 2 and 3 and FIGS. 1, 2, 3:

In the tables and FIGS. 1, 2 and 3, a “medium” filler has been used,that is leading in the “cone test”, to a diameter of 170 mm with notreating agent (left hand column) and to “galette”, whose aspect isindicated at the dosage of treating agent equally indicated (dosage isexpressed in % by weight of DRY treating agent/CaCO₃ by weight, DRY)after the self-levelling process. As discussed above, 170 mm is by farinsufficient.

Table 1 and FIG. 1 correspond to a surface treatment with thesuperplastifier A described above at a dosage of such as expressed inthe corresponding Table.

Table 2 and FIG. 2 correspond to a surface treatment with thesuperplastifier B described above at a dosage of such as expressed inthe corresponding Table.

Table 3 and FIG. 3 correspond to a surface treatment by the product NRG100 at a dosage such as expressed in the corresponding Table.

TABLE 1 “Medium” Filler Test N^(o) 2312/B 2312/B1 2312/B2 2312/B32312/B10 2312/B11 2248/1 2312/B12 2312/B21 Treatment Mode None postajout post ajout post ajout initial initial initial initial lödige 3 minTreatment Agent None A A A A A A A A Treatment Agent x 0.025% 0.05% 0.5%0.025% 0.05% 0.1% 0.5% 0.1% dosage - Dosage unit = weight treatmentAgent(s) dry/ weight Calcium Carbonate(s) dry “Galette” = 170 mm 238 mm306 mm 477 mm 280 mm 308 mm 442 mm 451 mm 435 mm diameter obtained inthe self- levelling cone test Result D1 C1 B1 A1 C1 B1 A1 A1 A1 VisualAspect Plastic Homogeneous Plastic Liquid// Homogeneous Plastic FluidFluid Fluid aspect but aspect aspect Fast aspect Aspect do not Spreadingspread

TABLE 2 “Medium” Filler Test N^(o) 2312/B 2312/B4 2312/B5 2312/B62312/B13 2312/B14 2312/B15 2312/B16 2312/B22 Treatment Mode None postajout post ajout post ajout initial initial initial initial lödige 5 minTreatment Agent None B B B B B B B A Treatment Agent x 0.025% 0.05% 0.5%0.025% 0.05% 0.1% 0.5% 0.1% dosage - Dosage unit = weight treatmentAgent(s) dry/ weight Calcium Carbonate(s) dry “Galette” = 170 mm 335 mm395 mm 457 mm 382 mm 390 mm 425 mm 441 mm 437 mm diameter obtained inthe self- levelling cone test Result D1 B1 A1 A1 A1 A1 A1 A1 A1 VisualAspect Plastic Plastic Fluid Liquid// Fluid Fluid Fluid Fluid Fluidaspect but aspect Fast do not Spreading spread

TABLE 3 “Medium” Filler Test N^(o) 2312/B 2312/B7 2312/B8 2312/B92312/B17 2312/B18 2312/B19 2312/B20 2312/B23 Treatment Mode None postajout post ajout post ajout initial initial initial initial lödige 5 minTreatment Agent None NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 NRG100NRG100 Treatment Agent x 0.025% 0.05% 0.5% 0.025% 0.05% 0.1% 0.5% 0.1%dosage - Dosage unit = weight treatment Agent(s) dry/ weight CalciumCarbonate(s) dry “Galette” = 170 mm 220 mm 383 mm 465 mm 328 mm 413 mm432 mm 451 mm 435 mm diameter obtained in the self- levelling cone testResult D1 C1 A1 A1 B1 A1 A1 A1 A1 Visual Aspect Plastic HomogeneousFluid Liquid// Plastic Fluid Fluid Fluid Fluid aspect but aspect FastAspect do not Spreading spread

In the three curves of FIGS. 1 to 3, the curve corresponding to anaddition of the superplastifier(s) AFTER all the other ingredients(COMPARATIVE, MUCH LESS PREFERRED MODE) is marked with “diamonds” (“postajout mode” in the Tables) while the “pre-treatment mode” or “initial”(laboratory version of the pre-treatment) curve” of the invention ismarked with “squares” (“initial mode” in the Tables).

The “triangle” in the Tables is an isolated point corresponding to a100% pretreatment of the filler in an outside mixing device as forexample LODIGUE, during 3 or 5 min., prior to its introduction in thekneading or mixing device (right hand column in the Tables, 435, 437 and435 mm for the “galette” in the cone test at only 0.1% dosage).

The said “triangle” is sometimes difficult to notice on the FIGS. 1-6because it superimposes with squares and/or diamonds, FIGS. 1 to 6 havebeen split into FIGS. 1a to 6a (curves) and FIGS. 1b to 6b (schematic,enlarged scale showing the approximate location of the superimposedmarks).

It was expected that for treating a coarser filler, the amount ofadjuvant(s) must be far or significantly higher. Quite surprisingly, thereverse occurs, that is, proportions such as from 0.03-0.05 to 0.1-0.5%are quite efficient.

We surprisingly note on the curves of FIGS. 1 and 2 (and from the %values in the corresponding Tables 1 and 2) the occurrence of a“plateau” at about 0.12% so that it is useless to incorporate more thatabout 0.1% of adjuvant.

The best range is therefore 0.1%-0.12%

To be noted, the study of the lower part of the curves, namely thatrelated to the treatment with B, shows that a clear technical effectappears at 0.03-0.05%: one can note a very steep increase in diameter(consistency) and this represents a threshold dosage (lower limit of therange) that is where the self-levelling (of the “galette” or cone)requirement of 250-300 mm is reached.

As to table 3 and FIG. 3, one can see that the “initial mode” curve isquite similar to those of FIGS. 1 and 2, that is a very clear “plateau”after 0.1-0.12%-0.20% or so, and a similar steep increase in consistencytowards the lower dosages, while the “post ajout” mode curve shows asimilar behaviour at the low dosages but (above 0.05% or so) shows aregular but slower increase. For that superplastifier A, one can seethat the useful range of dosage in the “initial mode” process is from0.05% (corresponds to 300 mm consistency) to 0.1-0.12%-0.20% (beginningof the clear “plateau”, like in curves 1 and 2); in contrast, with the“post ajout mode” curve, the lower dosage threshold is about the same(the two curves superpose at about 300 mm) while it is necessary to addabout 0.3% of product NRG 100 to reach about 425 mm, vs. about 0.1% forthe pre-treatment curve, or the Lödige point.

However, one can see that the “initial mode” curve allows to reach aplateau at 450 mm for about 0.1-0.12-0.15% of treating agent A used inthe process according to the invention, while B and NRG 100 were, forthe same % (and for the “initial mode” curve) at about 425 mm.

One can therefore say that a technical effect appears, depending on thecurves and on the desired value of consistency in mm) above0.02-0.03-0.05% superplastifier(s)/weight cement (dry), at which pointthat proportion of adjuvant(s) allows the system to be UNblocked; thisis the UNblocking point. This “unblocking point” is probably the key forthe unexpected effect of the process of the invention. Therefore, againdepending on the adjuvant and on the desired value of consistency, andfor THIS filler, one can deduce from the said “unblocking” point thatthe optimum proportion is at about 0.08-0.1-0.12-0.15% (since a“plateau” follows, so that there is no need to add more of expensiveadjuvant, for example no need to go up to 0.5%) AND it is mostpreferable to use a “INITIAL MODE or “pre-treatment” PROCESS”—that isthe process where the superplastifier(s) adjuvant(s) is/are added with(or at the same point of addition as) the filler (that is, the filler iseither first pre-treated with the superplastifier adjuvant in a separateequipment like the known LODIGE mixing device (but with no actual betterresult, see above the “triangle” points) or the superplastifier(s) (andoptionally the cost-reducing amount of plastifier(s)) is/are added alongwith the filler since it can be seen from the drawings FIGS. 1, 2 and 3that the “initial mode” or “pretreatment” curve is always better thanthe “post ajout mode” curve (that is when the treating agent is addedafter all the major ingredients including after the filler(s)).

It could even be risky to add more than the optimum 0.1-0.12-0.15%adjuvant/cement since there would be too much of adjuvants and thereforefree polymer (that is free adjuvant) would remain in the system. Thesaid excess of adjuvant (free polymer) could interact with cement, withother additives etc. and would be likely to unbalance the system.

Tables 4, 5, 6 and FIG. 4, 5, 6:

The principle and the procedures are the same as in Tables 1-3 andcorresponding FIGS. 1-3.

We attach Tables 4, 5 and 6 (corresponding to FIGS. 4, 5 and 6),representing the same trials as above but with a different filler havingthis time a very good behaviour at the cone test, already 288 mmdiameter untreated, and a non-sticky, non-thick and very fluidself-levelled cone or “galette”.

TABLE 4 “HP” Filler Test N^(o) 2312/A 2312/A1 2312/A2 2312/A3 2312/A102312/A11 2239/3b 2312/A17 Treatment Mode None post ajout post ajout postajout initial initial initial lödige 3 min Treatment Agent None A A A AA A A Treatment Agent x 0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1%dosage - Dosage unit = weight treatment Agent(s) dry/ weight CalciumCarbonate(s) dry “Galette” = 288 mm 235 mm 361 mm 426 mm 367 mm 400 mm414 mm 416 mm diameter obtained in the self- levelling cone test ResultB1 C1 B1 A1 A1 A1 A1 A1 Visual Aspect Compact// Homogeneous// PlasticFluid Fluid Fluid Correct Fluid but Sticky Compact aspect Spreading//settles Settles Plastic Aspect

TABLE 5 “HP” Filler Test N^(o) 2312/A 2312/A4 2312/A5 2312/A6 2312/A122312/A13 2239/9 2312/A18 Treatment Mode None post ajout post ajout postajout initial initial initial lödige 3 min Treatment Agent None B B B BB B B Treatment Agent x 0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1%dosage - Dosage unit = weight treatment Agent(s) dry/ weight CalciumCarbonate(s) dry “Galette” = 288 mm 235 mm 361 mm 426 mm 367 mm 400 mm414 mm 416 mm diameter obtained in the self- levelling cone test ResultB1 D1 B1 A1 A1 A1 A1 A1 Visual Aspect Compact// Slow Plastic Fluid FluidFluid but Fluid Fluid but Sticky Spreading aspect settles settles

TABLE 6 “HP” Filler Test N^(o) 2312/A 2312/A7 2312/A8 2312/A9 2312/A142312/A15 2312/A16 2312/A19 Treatment Mode None post ajout post ajoutpost ajout initial initial initial lödige 3 min Treatment Agent NoneNRG100 NRG100 NRG100 NRG100 NRG100 NRG100 NRG100 Treatment Agent x0.025% 0.05% 0.1% 0.025% 0.05% 0.1% 0.1% dosage - Dosage unit = weighttreatment Agent(s) dry/ weight Calcium Carbonate(s) dry “Galette” = 288mm 235 mm 361 mm 426 mm 367 mm 400 mm 414 mm 416 mm diameter obtained inthe self- levelling cone test Result B1 C1 A1 A1 A1 A1 A1 A1 VisualAspect Compact// Homogeneous Correct Fluid// Correct Correct CorrectFluid but Sticky aspect spreading// Compact// Spreading// Spreading//Spreading// settles Compact Settles Compact Compact Compact// Settles

As can be seen, there is a profound difference, for that kind of “goodor HP” filler, between the curves corresponding to the two differentprocesses.

However, it can be seen that for both types of curves there exists anupper optimum limit at about 0.1% superplastifier(s) adjuvant/drycement, while here-again, adjuvant A behaves slightly differently from Band NRG 100.

As said above, it must however be kept in mind that TWO properties MUSTbe met simultaneously so as to produce a HP or technical quality system:

-   -   High consistency that is, roughly speaking, high        fluidity/workability as can be seen via the self levelling test,        that is diameter above about 250-300 or better above 320-350 mm        (and compacity or density that is little porosity) AND        SIMULTANEOUSLY    -   a non sticky, not “thick” (that is, easy to “handle”), not        “plastic” (and evidently not “dry”) product, with no        decantation.

This can be seen from the above six tables.

For example, in Table 1 and 2 (medium (170 mm) filler+A or Bsuperplastifier), one can see that:

-   -   tests 2312/B1 and B4, both “post ajout mode”: with 0.025% of        adjuvant, the obtained system is good in diameter (335 mm) only        for 2312/B4 though inferior to a dosage at 0.05% (395 mm) BUT B4        forms a non usable product since it has a “plastic aspect”: the        second condition is NOT met, while B5 is “fluid” and is usable.        To the contrary, B1 has an homogeneous aspect at 0.05% but shows        only a 238 mm feature, insufficient.    -   tests 2312 B10 (“initial” that is “pretreatment mode”) and B13        (initial mode too): for the same dosage, 0.025%, the product B        Table 2 leads to a better diameter but above all leads to a        “fluid” product while B10 (forms only an homogeneous product. At        the same dosage, B4 with product B leads to a plastic product.

Among the “initial mode” tests B13 to B16, Table 2, we note that all thesystems are fluid, and the difference lies in an increase of thediameter (consistency) with the dosage.

LODIGE: if we compare 2312/B21 (use of a premix in a LODIGE device, at adosage of 0.1%, and if we compare with an initial mode with no LODIGE,at the same dosage of 0.1%, that is 2248/1 (Table 1), one can see thatboth are fluid and that the LODIGE brings a slightly lower diameter (435vs 442 mm) which evidently does not justify the use of the additionalequipment LODIGE.

Therefore, the “initial” or “pretreatment” mode is best performed byintroducing “simultaneously” the filler(s) and the treatment agent(s)that is at a very close point of addition in terms of location and time.

Each Table and curve can be analysed like above, and the skilled manwill be able to use those numerous data, using multiple parameters,different superplastifiers, two different types of filler (one medium at170 mm consistency, untreated, untreated, the other HP at 280 mmconsistency, untreated), and the two process modes, to “build” his ownsystem in view of the above parameters, his specific needs orrequirements.

“Mixed-Treatment” Test:

A laboratory test has been performed by duplicating test 2248/1 of Table1 (treatment dosage 0.1%) except that the treatment has been performedon the filler by adding 50% (0.05%) of the efficient amount ofsuperplastifier A to the whole amount of filler (GCC “medium” quality)and mixing both products in a laboratory mixer, then rapidly introducingthe remaining 50% of superplastifier into the kneading or mixing devicethen introducing 5 s later the filler treated outside by the first 50%of superplastifier A. The diameter in the self levelling test was 392mm, and the aspect “fluid”; therefore one can consider that a mixedtreatment is slightly inferior in diameter, but is clearly part of theinvention.

The whole range of addition of the superplastifier(s) (and optionally ofthe cost-reducing amount of plastifier(s) can therefore, in view of allthe above tests and curves, and general information given in thisapplication, be defined as:

From 0.02-0.03-0.05% to 0.08-0.1-0.12-0.15% adjuvant(s)/dry weight ofcement

with easy adjustment by the skilled man.

One can see that all the objectives of the invention, that is the needsand requirements of the MODERN INDUSTRY, are met:

-   -   at a low dosage (hence at a low cost) of surface treatment by at        least one of the adjuvants described above,    -   with no need of using extra equipment,    -   medium to poor behaving fillers (rejected in the prior art or        treated at unreasonable costs and investments) can be easily        upgraded to HP fillers capable of forming with the other usual        ingredients    -   cement or mortar or concrete compositions or systems    -   which are of the “technical” grade, with a High to very High        consistency, above 250, 300, or even above 350 mm in the self        levelling standardized test, a High to very High compacity        (density), a high to very high % of dry material in the end        product, from 87 to 95%, by weight, of dry material in the        final, complete system.    -   what provides the skilled man not only with the possibility of        meeting the most stringent and recent industrial requisites, but        also to obtain products featuring for the first time a        “regularity” in the properties, that is predictability.

That “regularity” is a novel property which was not reached by far inthe prior art, despite the demand by the industry; it is believed,without being tied by a theory, that the process steps and the usedsuperplastifiers are responsible for this “regularity”.

The follow-up of the “regularity” is possible by adjusting the dosage ofthe A and B above surface-treatment products, or by selecting otherproducts as described hereabove, and adjusting the dosage, using theabove described test method to ensure that the properties remainconstant, what is called “regularity”.

Application(s)

The applications are all those commonly using the above describedcement, mortar, or concrete compositions or systems.

Cement Products

Those are the products or elements that are known to be manufacturedfrom the above cement, mortar or concrete compositions, in the buildingindustry or any other industry, in a well-known manner.

The invention claimed is:
 1. A cement composition comprising (i) cement,(ii) calcium carbonate surface treated with 0.02 to 0.15 wt. %, based onthe dry weight of the cement composition, of a treatment agentcomprising at least one superplasticizer and at least one plasticizer,wherein the ratio of the superplasticizer and the plasticizer is from95/5 to 85/15 on a dry weight basis, and wherein the calcium carbonateis surface treated with the treatment agent before being introduced intothe cement composition, and (iii) optionally one or more of anaggregate, sand, gravel, a hydraulic binder, an air entrainment agent, asetting retarder, a setting accelerator, an anti-foam agent, anadjuvant, a fluidifier and water.
 2. The cement composition according toclaim 1, wherein the calcium carbonate is calcium carbonate, groundcalcium carbonate, precipitated calcium carbonate or a blend of groundcalcium carbonate and precipitated calcium carbonate.
 3. The cementcomposition according to claim 1, wherein the superplasticizer isselected from the group consisting of a polycarboxylate, apolycarboxylate ether, a sulfonated naphthalene condensate, and asulfonated melamine formaldehyde.
 4. The cement composition according toclaim 1, wherein the superplasticizer is a polycarboxylate or apolycarboxylate ether.
 5. The cement composition according to claim 1,wherein at least 80% of the surface of particles of calcium carbonate iscovered with the at least one superplasticizer.
 6. The process accordingto claim 1, wherein at least 90% of the surface of particles of calciumcarbonate is covered with the at least one superplasticizer.
 7. Thecement composition according to claim 1, wherein 100% of the surface ofparticles of calcium carbonate is covered with the at least onesuperplasticizer and the plasticizer.
 8. The cement compositionaccording to claim 1, containing 0.3 to 3 kg of the at least onesuperplasticizer per 100 kg of the cement composition.
 9. The cementcomposition according to claim 1, containing 0.8 to 1.2 kg of the atleast one superplasticizer per 100 kg of the cement composition.
 10. Thecement composition according to claim 1, further comprising anaggregate, a hydraulic binder, an air entrainment agent, a settingretarder, a setting accelerator, an anti-foam agent, an adjuvant, and afluidifier.
 11. The cement composition according to claim 1, furthercomprising an aggregate, a hydraulic binder, an air entrainment agent, asetting retarder, a setting accelerator, an anti-foam agent, anadjuvant, a fluidifier, and water.
 12. The cement composition accordingto claim 1, further comprising an aggregate, sand, a hydraulic binder,an air entrainment agent, a setting retarder, a setting accelerator, ananti-foam agent, an adjuvant, and a fluidifier.
 13. The cementcomposition according to claim 1, further comprising an aggregate, sand,a hydraulic binder, an air entrainment agent, a setting retarder, asetting accelerator, an anti-foam agent, an adjuvant, a fluidifier andwater.
 14. The cement composition according to claim 1, furthercomprising an aggregate, sand, gravel, a hydraulic binder, an airentrainment agent, a setting retarder, a setting accelerator, ananti-foam agent, an adjuvant, and a fluidifier.
 15. The cementcomposition according to claim 1, further comprising an aggregate, sand,gravel, a hydraulic binder, an air entrainment agent, a settingretarder, a setting accelerator, an anti-foam agent, an adjuvant, afluidifier and water.
 16. The cement composition according to claim 2,further comprising an aggregate, a hydraulic binder, an air entrainmentagent, a setting retarder, a setting accelerator, an anti-foam agent, anadjuvant, and a fluidifier.
 17. The cement composition according toclaim 2, further comprising an aggregate, a hydraulic binder, an airentrainment agent, a setting retarder, a setting accelerator, ananti-foam agent, an adjuvant, a fluidifier, and water.